Textile lubricants



Patented Sept. 23, 1 958;

TEXTILE LUBRICANTS Maurice Elton, Sidcup, and Philip Alan Winsor, Willing ton, Kelsall, England, assignors to Shell Development Company, New York, N. 11, a corporation of Delaware N Drawing. Application March 14, 1955 Serial No. 494,256

Claims priority, application Great Britain March 29, 1954 7 Claims. c1. 2s2-a.7s

The present invention relates to lubricants for textiles and to a method of lubricating textile fibers. More particularly, it relates to emulsifiable and water emulsion textile lubricants and to the lubrication of textile fibers therewith during spinning and the like.

'Numerous commercially available textile lubricants have one or more defects which mitigate against thei use. For example, animal and vegetable fatty 0113 which areemplo-yed in some textile oils are expensive and tend to become rancid. Mineral oils are difficult to wash or scour out of the finished fiber, while various textile emulsions lack entirely satisfactory stability, lubricity and anti-static properties.

Recent work by H. L. Roder reported at a Symposium held on behalf of the Dutch Physical Society at Arnhem on October 5-6, 1950, has shown that the efiiciency of a lubricant for a given fiber can be measured by both the absolute and the relative values of the static and dynamic coefiicients of friction of the lubricated fibers against each other.

It appears from Roders work that only when the static coefiicient of friction is greater than the dynamic coeflicient of friction is satisfactory processing obtained since only then is the handle known as scroop exhibited. It is generally recognized that a certain degree of scroop facilitates satisfactory processing of fibers, particularly during carding.

When the static coefficient of friction is less than the dynamic coefficient of friction, or even when equal to it, the lubricated fibers possess little or no resistance to slipping with the result that they shift and slip constantly during processing and are therefore difiicult if not impossible to process satisfactorily.

It has now been discovered that an improved textile lubricant, whose static coefficient of friction exceeds its dynamic coeflicieut of friction, is provided by an emulsifiable concentrate comprising a major proportion of a mineral lubricating oil and minor proportions each, of an oil-soluble organic sulfonate, an oil-soluble non-ionic emulsifier and a nitrogenous emulsifier which is soluble in oil but substantially insoluble in water. Each of these additives should be present in the following proportions in the oil concentrate: sulfonates, from about 2% to about non-ionic emulsifier, from about0.5% to about 10% and the nitrogenous emulsifier from about 1% to about 13% by weight. The amount of nitrogenous emulsifier used is governed by the amount of sulfonate present in the blend. By properly adjusting their proportions the static coefiicient of friction can be maintained greater than the dynamic coefiicient of friction. Generally, the nitrogenous emulsifier is used in amounts equal to about one-half of the amount of sulfonate used in the blend.

To facilitate subsequent dilution with water and to assist coupling of the various components, the concentrates of the invention preferably contain a minor proportion of water, for example, up to 10% and preferably about 1 to 5% by weight of the composition.

These concentrates may be used as such or they may be used in the form of aqueous emulsions obtained on diluting them with from about 19 to 99 volumes of water. Preferably, aqueous emulsions containing about 2% by volume of the concentrate (dilution with 49 volumes of water) are used. Emulsification usually occurs spontaneously on diluting with water and the aqueous emulsions have very high stability. The aqueous emulsions are included within the scope of the invention.

The emulsifiable compositions of the invention are preferably so constituted as by the incorporation of a water-soluble inorganic base, that an emulsion containing 2 parts by volume thereof in 98 parts by volume'of distilled water has a pH value greater than 7, preferably greater than 9.

The mineral lubricating oil used in the compositions of the invention may be of any type. It may be a lightly refined oil, such as has been refined by distillation, solvent extraction, clay treatment or treatment with dilute acid or other chemical, or a highly refined oil, such as has been treated with fuming sulfuric acid, withor without prior solvent extraction. The oils may be, highly parafiinic oils containing at least 65% by weight of material remaining unsulfonated when treated with concentrated sulfuric acid, or may contain naphthenic and aromatic constituents. For use in textile oil compositions, highly refined oils are preferred because of their greater stability and resistance to the development of odor and col-or on exposure to light and air; they should have a flash point sufiiciently high to satisfy the requirements of any particular section of the industry. Thus, in the worstedand woolen trades, a minimum flash point of 340 F. is required.

The oil-soluble sulfonates used in the compositions of this invention can be of various types such as neutral and/ or basic and can be derived from any suitable material and prepared by any of the well-known suitable methods.

Preferred materials for making oil-soluble sulfonates include mineral lubricating oil fractions, alkyl-substituted aromatic compounds and alkyl-substituted polar containing aromatic compounds. Petroleum sulf-onates suitable for use in compositions of this invention are described in United States Patents 2,280,419, 2,344,988, 2,361,804, 2,375,222, 2,480,638, 2,485,861, 2,509,863, 2,501,731, 2,523,582 and 2,585,520. The sulfonates can'be purified by the methods described in United States Patents 2,441,258 and 2,488,721. Suitable aromatic sulfonates include those described in United States Patents 2,411,583, 2,418,894, 2,442,915, 2,483,501, 2,531,324, 2,556,108 and 2,556,848. Although various metal sulfonates are contemplated in the practice of the invention, including alkali metal sulfonates, alkaline earth metal sulfonates (including magnesium) and other polyvalent metal sulfonates, the nitrogen base sulfonates obtained by treating sulfonic acids with ammonia orv an amine such as aliphatic amines or alkylolamines such as triethanolamine also can be used. Specific sulfonates which are suitable for use in compositions of this' invention include: Na, K, Li, Ca, Ba, Mg, ammonia, triethanolamine petroleum sulfonate, tetra-tertiary-butylnaphthalene sulfonate, diwaxbenzenesulfonate, stearylbenzenesulfonate, diwaxnaphthalenesulfonate, diisobutylencphenolsulfonatc, tertiaryctylphenol sulfonate, ditertiary-amylphcno-l sulfonate, alkylated-dibcnzothiophene sulfonate and mixtures thereof. Preferred are thes a'lts of these acids in which the cationicportion is a water, soluble base of a monovalent cation.

Preferred sulfonates for use in compositions of thisinvention are obtained as a by-product during the menu:

(It facture of technical white oil and transformer oil. Treatment of the appropriate feed stock with oleum results in the formation of a lower acid sludge layer and an upper oil layer containing oil-soluble petroleum sulfonic acids or mahogany acids. These petroleum sulfonic acids may be isolated by treating the oil layer with a solution of an alkali metal hydroxide or with ammonia or an aliphatic amine or alkylolamine such as triethanolamine and the crude salts thus obtained purified if desired. The

petroleum sulfonic acids whose salts are used in the compositions of the invention preferably have an average molecular weight of from 420 to 450, although they can be as much as 350 to as high as 600, the sodium petroleum sulfonates which are available commercially being preferred.

A wide variety of compounds may be used as the oilsoluble non-ionic emulsifier. These compounds are preferentially oilsoluble but may also be soluble in water to a minor extent. Suitable compounds are those containing an alcoholic hydroxyl group and the following classes of compounds have proved effective:

(I) Oil-soluble monohydric alcohols, e. g., the octanols, nonanols, decanols, undecanols, dodecanols and the higher aliphatic alcohols. These may be synthetic alcohols, e. g., alcohols produced by the so-called Oxo process, or they may be of natural origin, e. g., fatty alcohols from sperm oil. Also oil-soluble aromatic and cycle aliphatic alcohols such as benzyl alcohol and methylcyclohexanol may be used.

(II) Oil-soluble dihydric alcohols such as the hexylene glycols, octylene glycols, decylene glycols and the higher glycols.

(III) Oil-soluble alcohols containing substituents such as ether and/or ester groups. Particularly effective members of this class are the partial esters of polyhydric al cohols and fatty acids such as glycerol monoor di-oleate or stearate, ethylene glycol mono-oleate or stearate and the mono-esters of ethers of polyethylene glycols such as the mono-oleate or stearate of nonaethylene glycol. Compounds such as glycerol di-oleate have the valuable property of lowering the friction values of the compositions.

A single oil-soluble non-ionic emulsifier may be employed but it is often useful to use a mixture of two or more such compounds in order to obtain optimum scourability and spontaneity of emulsion formation. Thus, a mixture of glycerol dioleate and a minor proportion of diglycol laurate, and a mixture of glycerol dioleate with minor proportions of diglycol laurate and nonaethylene glycol mono-oleate have been found particularly effective.

The nitrogenous emulsifier which is used in the compositions of the invention is soluble in mineral oil but substantially insoluble in water.

Suitable nitrogenous emulsifiers of this type are the primary, secondary and tertiary amines containing at least one hydrophobic group attached to the nitrogen atom, for example, dodecylamine, octadecylamine, dicetylamine, N- octadecyl-N-hydroxyethylamine, N-alkyl-N-hydroxypropylpiperidines in which the alkyl radicals are derived from coconut oil and the mono-acyl or as-diacyl derivatives of aliphatic polyamines such as oleyl ethylenediamine and as-distearylethylene diamine. Particularly suitable nitrogenous emulsifiers for use in the compositions of the invention are the organic compounds free from sulfonic acid groups which contain the atomic grouping The 4 iminazoles, imidazolines and pyrimidines. Specific examples of such compounds are O-ethylurea, S-dodecylthiourea, 1-guanidino-palmitic acid, lhydroxyethylguanidine, 2-undecylimidazoline, 1-/3-hydroxyethyl-2-heptadecyleneimidazoline, Z-naphthenyl-imidazoline, 2-heptadecylbenziminazole, Z-undecylpyrimidine and l-benzyl-Z- heptadecylbenziminazole, of preferred are l-fl-hydroxyethyl-Z-heptadecyleneimidazoline and Z-naphthenyl-imidazoline. Salts of such compounds with inorganic or organic acids such as hydrochloric acid, acetic acid, stearic acid or oleic acid may also be used. Mixtures of these nitrogenous emulsifiers may be employed.

When the compositions of the invention are intended for use as textile fiber lubricants, the proportion of nitrogenous emulsifier present is dependent to a large extent on the content of petroleum sulfonate.

Sulfonates such as sodium petroleum sulfonate have the desirable property of promoting the formation of emulsions of very fine particle size which, in consequence, are translucent or clear. Simple emulsions of water, oil and sulfonate, however, have an undesirably high coeflicient of friction when they are used as textile fiber lubricants, particularly for nylon and nylon-type fibers.

Addition of the nitrogenous emulsifier promotes emulsion stability and produces compositions which lower the coefiicients of inter fiber friction. If present in too high concentration relative to the quantity of sulfonate in the blend, however, the nitrogenous emulsifier will cause the dynamic coefficient of inter fiber friction to become greater than the static coefficient of friction with consequent unsatisfactory processing of the lubricated fibers. When the compositions of the invention are intended for use as lubricants, particularly as textile fiber lubricants, the amount of nitrogenous emulsifier present should be just sufiicient to produce a composition of suitable frictional properties, i. e., with a static coefficient of friction greater than the dynamic coefficient of friction.

In addition to the aforementioned essential ingredients, other substances having particular properties may be incorporated in minor amounts in the compositions of the invention.

Thus, it may be desirable to incorporate a coupling agent or mutual solvent to aid in solubilizing the ingredients, in promoting spontaneous emulsion formation, and in stabilizing the emulsion. Such substances include mon-ohydric alcohols containing less than 8 carbon atoms in the molecule, for example, isopropyl alcohol, butyl and amyl alcohols, cyclohexanol, diacetone alcohol, phenols, the glycols, such as hexylene glycol, and polyethylene lycol and glycol mono-ethers such as the ethyl or butyl ether of ethylene glycol.

If desired, other anionic emulsifiers rnay be incorporated in minor amounts in the compositions of the invention, as for example, the alkali metal soaps of higher fatty acids and rosin acids, alkali metal salts of sulfuric acid esters of higher primary and secondary alcohols and alkali metal salts of alkyl aryl sulfouates. These assist spontaneity of emulsion formation on dilution with water.

Anti oxidants are also desirable additional ingredients in the compositions of the invention, for example, 2,4-

dimethyl-6-tertiary butyl phenol, N-butyl para phenylene diamine, tetramethyl-diaminodiphenyl methane.

Small proportions of anti-foaming agents such as silicones and fine dispersions of N,N-distearyl ethylene diamine or N,N- distearyl hexamethylene diamine in mineral oil may also advantageously be incorporated.

When the compositions of the invention are to be used as textile oils, it may also be desirable to incorporate small proportions of compounds which will inhibit the growth of mildew on the wetted fibers. Salicylanilide is a suitable fungicide for this purpose.

Corrosion inhibitors may also be incorporated in the invention. Compounds which are particularly suitable are the primary amines containing from 6 to 15; carbon atoms in the molecule, such as octylamine and octadecylamine and the heterocyclic nitrogen containing organic compounds such as the alkyl substituted oxazolines and the oxazoline salts of fatty acids.

The following examples illustrate the compositions of the invention, the parts referred to being by weight:

Example I A blend was prepared from 63 parts of spindle oil, 4.9 parts of 1-fi-hydroxyethyl-2-heptadecylene imidazoline, 4.9 parts of glycerol dioleate, 1.2 parts of diglycol laurate, 9.8 parts of oil-soluble sodium petroleum sulfonates (molecular weight 420-450), 6.5 parts of colophony rosin, 3.3 parts of oleic acid, 1.2 parts of potassium hydroxide, 2.6 parts of isopropyl alcohol and 2.6 parts of water.

This was a satisfactory finishing oil for viscose rayon when used as a 2% vol./vol. aqueous emulsion.

Example 11 This blend was prepared from 54.6 parts of spindle oil, 4.8 parts of 1-fi-hydroxyethyl-2-heptadecylene imidazoline, 4.8 parts of glycerol dioleate, 0.6 part of diglycol laurate, 13.0 parts of oil-soluble sodium petroleum sulfonates (molecular weight 420-450), 8.7 parts of colophony rosin, 4.4 parts of oleic acid, 2.1 parts of potassium hydroxide, 3.5 parts of isopropyl alcohol and 3.5 parts of water.

This blend readily emulsified with water to give a clear oil-in-water emulsion, which was unchanged after 2 weeks storage.

A 2% vol./vol. emulsion in distilled water had a pH of 10.9. When this aqueous emulsion was used for lubricating nylon 66 filaments, the static coefficient of friction was 0.185 and the dynamic coefficient of friction was 0.175, when measured by the Roder method referred to above.

Example III This blend was prepared from 57.7 parts of spindle oil, 4.6 parts of 1- 3-hydroxyethyl-2-heptadecylene imidazoline, 4.6 parts of glycerol di-oleate, 1.1 parts of diglycol laurate, 5.4 parts of glycol monooleate, 10.0 parts of oilsoluble sodium naphthasulfonates (molecular weight 420-450), 6.5 parts of colophony rosin, 3.3 parts of oleic acid, 1.6 parts of potassium hydroxide, 2.6 parts of isopropyl alcohol and 2.6 parts of water.

This blend was a satisfactory knitting medium for sized nylon fibers when used as a 2% vol./vol. aqueous emul- SlOIl.

The compositions of the invention may be applied to textile fibers by any of the well-known methods, for example, by spraying running textile yarns or by running textile yarns through baths or over wicks or other similar devices from which they pick up the composition in emulsion form as described above. Alternatively the textile yarns may be dipped in baths containing the composition.

We claim as our invention:

1. An anti-static emulsifiable textile lubricant concentrate composition comprising a major amount of mineral lubricating oiland containing from about 2% to about 20% by weight of an oil-soluble sodium petroleum sulfonate, from about 0.5% to about 10% by weight of an oil-soluble partial ester of a polyhydric alcohol with a fatty acid, from about 1% to about 13% of l-fl-hydroxyethyI-Z-heptadecylene-imidazoline and from about 1% to about 10% of water.

2. An anti-static emulsifiable textile lubricant concentrate composition comprising a major amount of mineral lubricating oil and containing from about 2% to about 20%by weight of an oil-soluble sodium petroleum sulfonate, from about 0.5% to about 10% by weight of an oil-soluble partial ester of a polyhydric alcohol with a fatty acid, from about 1% to about 13%v of 2- naphthenylimidazoline and from about 1% to about 10% of water.

3. An anti-static emulsifiable textile lubricant c centrate composition comprising a major amount of mineral lubricating oil and containing from about 2% to about 20% by weight of an oil-soluble sodium petroleum sulfo-nate, from about 0.5 to about 10% by weight of glycerol dioleate, from about 1% to about 10% iby weight of water and from about 1% to about 13% of l-,B- hydroxyethyl-Z-heptadecyleneimidazoline.

4. An anti-static emulsifiable textile lubricant concentrate composition comprising about 4.8 parts of 1-[3- hydroxyethyl-Z-heptadecyleneimidazoline, about 4.8 parts of glycerol dioleate, about 0.6 parts of diglycol laurate, about 13 parts of oil-soluble sodium petroleum sulfonate, about 8.7 parts of colophony rosin, about 4.4 parts of oleic acid, about 2.1 parts of potassium hydroxide, about 3.5 parts of isopropyl alcohol, about 3.5 parts of water and about 54.6 parts of spindle oil.

5. The composition of claim 4 diluted with from 19 to 99 volumes of water.

6. An anti-static emulsifiable textile luibricant concentrate composition comprising a major amount of mineral lubricating oil and containing from about 2% to about 20% by weight o-f an oil-soluble alkali metal petroleum sulfonate, from about 0.5 to about 10% by weight of an oil-soluble partial ester of a polyhydric alcohol with a higher fatty acid, from about 1% to about 13% of an oil-soluble hydrocarbon-substituted.imidazoline and from about 1% to about 10% of water. I

7. The composition of claim 6 diluted with from 19 to 99 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS Winsor Jan. 10, 1956 

1. AN ANTI-STATIC EMULSIFIABLE TEXTILE LUBRICANT CONCENTRATE COMPOSITION COMPRISING A MAJOR AMOUNT OF MINERAL LUBRICATING OIL AND CONTAINING FROM ABOUT 2% TO ABOUT 20% BY WEIGHT OF AN OIL-SOLUBLE SODIUM PETROLEUM SULFONATE, FROM ABOUT 0.5% TO ABOUT 10% BY WEIGHT OF AN OIL-SOLUBLE PARTIAL ESTER OF A POLYHYDRIC ALCOHOL WITH A FATTY ACID, FROM ABOUT 1% TO ABOUT 13% OF 1-B-HYDROXYETHYL-2-HEPTADECYLENE-IMIDAZOLINE AND FROM ABOUT 1% TO ABOUT 10% OF WATER. 